WO1993013053A2 - Isomerisation process - Google Patents
Isomerisation process Download PDFInfo
- Publication number
- WO1993013053A2 WO1993013053A2 PCT/GB1992/002323 GB9202323W WO9313053A2 WO 1993013053 A2 WO1993013053 A2 WO 1993013053A2 GB 9202323 W GB9202323 W GB 9202323W WO 9313053 A2 WO9313053 A2 WO 9313053A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- isomer
- epimer
- enantiomer
- cyanide
- racemate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000006317 isomerization reaction Methods 0.000 title description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 4
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 claims description 9
- 239000005910 lambda-Cyhalothrin Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000005652 Acrinathrin Substances 0.000 claims description 3
- 239000005892 Deltamethrin Substances 0.000 claims description 3
- YLFSVIMMRPNPFK-WEQBUNFVSA-N acrinathrin Chemical compound CC1(C)[C@@H](\C=C/C(=O)OC(C(F)(F)F)C(F)(F)F)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 YLFSVIMMRPNPFK-WEQBUNFVSA-N 0.000 claims description 3
- -1 alkali metal cyanide Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 3
- 229960002483 decamethrin Drugs 0.000 claims description 3
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 claims description 3
- 239000002728 pyrethroid Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 239000000047 product Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZXQYGBMAQZUVMI-UNOMPAQXSA-N cyhalothrin Chemical compound CC1(C)C(\C=C(/Cl)C(F)(F)F)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-UNOMPAQXSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
- C07C255/39—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups with hydroxy groups esterified by derivatives of 2,2-dimethylcyclopropane carboxylic acids, e.g. of chrysanthemumic acids
Definitions
- This invention relates to a process for converting a first isomer into a second isomer wherein the first and second isomers are epimers of the same compound.
- the present invention provides a process for obtaining an isomer of a compound of general formula
- each of R and R' may be any organic radical linked directly or through a heteroatom to the carbon atom bearing the cyano group provided that at least one of R and R' comprises at least one resolved chiral centre which is stable under the conditions of the process, or a racemic modification comprising the isomer and its enantiomer, which comprises the step of treating the epimer of the isomer, or the racemate comprising the epimer and the enantiomer of the epimer, in solution in a polar organic solvent, or in slurry in a polar organic liquid diluent in which the epimer or the racemate is partially soluble, with a source of cyanide ions, in the absence of a base, the isomer, or the racemic modification comprising the isomer and its enantiomer, being less soluble in the solvent or diluent than the epimer of the isomer, or the racemate comprising the epimer of the isomer and the enantiomer of the epimer, respectively.
- the process of the invention provides a means to obtain the isomer from its epimer where the epimer has been obtained by a production process in admixture with the isomer, and similarly it provides a means to obtain the racemic modification comprising the isomer and its enantiomer from the racemate comprising the epimer and the enantiomer of the epimer where the racemate has been obtained by. a production process in admixture with the isomer and its enantiomer.
- ester compounds may be found many which are useful as insecticides, such as for example, those wherein R is selected from 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropylcarbonyloxy, 3-(2-optionally substituted phenyl-2-halovinyl)-2,2-dimethylcyclopropylcarbonyloxy, 3-(2-haloalkyl-2-halovinyl)-2,2-dim thylcyclopropylcarbonyloxy, 3-(2,2-dialkylvinyl)-2,2-dimethylcyclopropylcarbonyloxy, 3-(2-optionally substituted alkoxycarbonylvinyl)-2,2-dimethylcyclopropylcarbonyloxy, 3-(2-optionally substituted alkoxycarbonyl-2-halovinyl)-2,2- -dimethylcyclopropylcarbonyloxy, and 2-(optio ⁇ ally substituted phenyl)alkanoyloxy, and R' is selected from 3-(2,
- Pyrethroids are usually obtained by esterification processes which yield mixtures of isomers. It is known that some isomers have a greater insecticidal effect than others, and this has led to the development of techniques to separate the more active isomers, and to convert the less active isomers into the more active. Such processes have been described in for example UK patent no. 1582594, European patent no. 107296 and US patent no. 4997970, and are all characterised by the use of a base.
- the base not only promotes the desired isomerisation by way of proton removal leading to epimerisation at the carbon atom bearing the cyano group but also, unfortunately, can catalyse the decomposition of the esters, leading to lowered yields of the desired product.
- the invention process can be used to obtain deltamethrin, acrinathrin, S-fenvalerate and lambda-cyhalothrin from precursors products in which the desired isomer or racemate is admixed with its epimer or epimer racemate without the danger of loss of yield through base catalysed decomposition.
- the process appears to operate on a reduced cycle time indicating that the use of cyanide mediated isomerisation offers an unexpected but significant economic advantage in comparison with the known base-catalysed epimerisation processes.
- the polar organic solvents or diluents which may be used for the invention process are those in which the product isomer or racemic modification is less soluble than the epimer or racemate thereof.
- These may be for example onohydric lower alkanols containing up to six carbon atoms, such as isopropanol, isobutanol and jt-butanol, or mixtures thereof.
- Other solvents or diluents include simple esters, such as ethyl acetate or mixtures with alkanes to obtain a medium which permits the isomer and the epimer to be separated on the basis of solubility difference. A proportion of water may be present, within the limits of miscibility, but this is usually less than 20% by volume.
- the solvent is a branched lower alkanol such as isopropanol containing from 2 to 15% by volume of water.
- the source of cyanide ions may be an alkali or alkaline earth cyanide, or a quaternary ammonium cyanide.
- Sodium cyanide and potassium cyanide are particularly preferred. It may be used in solid form, in which case any residual material at the conclusion of the process must be separated from the solid product by selective solubility, either by washing with water to dissolve the cyanide, or by extraction with an organic solvent to dissolve the product.
- the cyanide may be in the form of -an aqueous solution, which if used in excess may give rise to a two-phase system when certain solvents are used, in which case the process may be facilitated by the use of phase-transfer catalysts, such as the aforementioned quaternary ammonium cyanide.
- the cyanide is present in an amount of from 0.5 to 15 mole X of the epimer.
- One convenient technique for isolating the product is to discharge the contents of the reaction vessel into an excess of dilute aqueous acid, such as sulphuric acid, or preferably a dilute aqueous solution of an alkali metal hypochlorite.
- This technique can be used with reaction mixtures involving cyanide in either solid or solution form, and permits recovery of the product by either filtration or solvent extraction.
- the process is conducted in vessels in which the temperature may be controlled by external heating or cooling.
- the rate of deposition of the crystalline product is enhanced by reducing the solubility of the product by operating at lower temperatures, and by agitation of the vessel contents so as to provide thorough mixing.
- the period over which the process is conducted will depend upon the rate at which the product is formed, but is unlikely to be less than one hour or more than 60 hours.
- the precise conditions required will vary according to the particular product, but in general the process may be operated at a temperature in the range -10°C to 20°C for a period of from 15 to 45 hours.
- the process can be conducted merely by adding the cyanide to a solution of the epimer and agitating the mixture at the relevant temperature for a period, it is often helful, especially for products having lower melting points or relatively higher solubility, to add a quantity of the product in solid crystalline form to the mixture so as to provide a crystalline surface on which further product can crystallise.
- the amount of added crystalline product is not critical provided that it is sufficient to provide a saturated solution with some remaining in the undissolved state at the particular operating temperature.
- lambda-cyhalothrin is a racemic product consisting of the isomer S- ⁇ -cyano-3-phenoxybenzyl lR,3R-3-(Z-2- chloro-3,3,3-trifluoroprop-l-en-l-yl)-2,2-cyclopropane carboxylate and its enantiomer.
- Lambda-cyhalothin is obtained from cyhalothrin, which is produced as a mixture of four isomers in approximately equal amounts, the two isomers constituting lambda-cyhalothrin and the epimers of these two isomers, that is R- ⁇ -cyano-3-phenoxybenzyl IR,3R-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-l-yl)-
- Cyhalothrin (105g), wet isopropanol containing 2.7 or 8.0% w/w water (270g), sodium cyanide (6.5g), and crystalline lambda-cyhalothrin are charged to a 1-litre glass vessel fitted with an twin turbine glass agitator and a cooling jacket and maintained at a temperature of -5°C by circulation of a cooled mixture of water and ethylene glycol with agitation for a period of 24 hours after which the ratio of Isomer Pair I/Isomer Pair II was determined by a gas chromatographic technique. The agitation is continued for a further 24 hours an a second determination of the I/II ratio made.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Steroid Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Lubricants (AREA)
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE69213761T DE69213761T2 (de) | 1991-12-24 | 1992-12-15 | Isomerisierungsverfahren |
| SK760-94A SK281750B6 (sk) | 1991-12-24 | 1992-12-15 | Spôsob prípravy izoméru |
| JP51123493A JP3490083B2 (ja) | 1991-12-24 | 1992-12-15 | 異性化方法 |
| RO94-01080A RO114125B1 (ro) | 1991-12-24 | 1992-12-15 | Procedeu de izomerizare |
| EP92924842A EP0618896B1 (en) | 1991-12-24 | 1992-12-15 | Isomerisation process |
| CA002126180A CA2126180C (en) | 1991-12-24 | 1992-12-15 | Isomerisation process |
| RU94031154A RU2129536C1 (ru) | 1991-12-24 | 1992-12-15 | Способ получения лямбда-цигалотрина изомеризацией |
| BR9206983A BR9206983A (pt) | 1991-12-24 | 1992-12-15 | Processo para a obtenção de um isômero de um composto |
| AU30932/92A AU679168B2 (en) | 1991-12-24 | 1992-12-15 | Isomerisation process |
| KR1019940702213A KR100249399B1 (ko) | 1991-12-24 | 1992-12-15 | 이성질화 공정 |
| UA94005435A UA39862C2 (uk) | 1991-12-24 | 1992-12-15 | Спосіб отримання ізомеру або рацемічної модифікації, що містить ізомер та його енантіомер |
| FI942989A FI114465B (fi) | 1991-12-24 | 1994-06-21 | Menetelmä pyretroidi-insektisidiyhdisteen aikaansaamiseksi |
| NO942400A NO300678B1 (no) | 1991-12-24 | 1994-06-23 | Isomeriseringsprosess |
| BG98874A BG61446B1 (en) | 1991-12-24 | 1994-06-24 | Method for isomerization |
| GR960402622T GR3021271T3 (en) | 1991-12-24 | 1996-10-07 | Isomerisation process. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9127355.7 | 1991-12-24 | ||
| GB919127355A GB9127355D0 (en) | 1991-12-24 | 1991-12-24 | Isomerisation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1993013053A2 true WO1993013053A2 (en) | 1993-07-08 |
| WO1993013053A3 WO1993013053A3 (en) | 1993-08-05 |
Family
ID=10706802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1992/002323 WO1993013053A2 (en) | 1991-12-24 | 1992-12-15 | Isomerisation process |
Country Status (26)
| Country | Link |
|---|---|
| US (1) | US5334744A (ko) |
| EP (1) | EP0618896B1 (ko) |
| JP (1) | JP3490083B2 (ko) |
| KR (1) | KR100249399B1 (ko) |
| AT (1) | ATE142617T1 (ko) |
| AU (1) | AU679168B2 (ko) |
| BG (1) | BG61446B1 (ko) |
| BR (1) | BR9206983A (ko) |
| CA (1) | CA2126180C (ko) |
| CZ (1) | CZ287245B6 (ko) |
| DE (1) | DE69213761T2 (ko) |
| DK (1) | DK0618896T3 (ko) |
| ES (1) | ES2091497T3 (ko) |
| FI (1) | FI114465B (ko) |
| GB (2) | GB9127355D0 (ko) |
| GR (1) | GR3021271T3 (ko) |
| HU (1) | HU214673B (ko) |
| NO (1) | NO300678B1 (ko) |
| NZ (1) | NZ246081A (ko) |
| RO (1) | RO114125B1 (ko) |
| RU (1) | RU2129536C1 (ko) |
| SK (1) | SK281750B6 (ko) |
| TW (1) | TW318827B (ko) |
| UA (1) | UA39862C2 (ko) |
| WO (1) | WO1993013053A2 (ko) |
| ZA (1) | ZA929971B (ko) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0229803D0 (en) | 2002-12-20 | 2003-01-29 | Syngenta Ltd | Chemical process |
| KR101595456B1 (ko) | 2014-06-30 | 2016-02-19 | 대한민국 | 보안등의 가변식 차광기구 |
| KR101595453B1 (ko) | 2014-06-30 | 2016-02-19 | 대한민국 | 보안등의 고정식 차광기구 |
| CN107673996A (zh) * | 2017-09-28 | 2018-02-09 | 浙江工业大学 | 一种低活性氰戊菊酯异构体向高活性氰戊菊酯异构体转化的方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002289A1 (en) * | 1977-09-26 | 1979-06-13 | Shell Internationale Researchmaatschappij B.V. | Process for converting a stereoisomeric ester into its diastereoisomer; crystalline (-)-S-alpha-cyano-3-phenoxybenzyl (+)-S-alpha-isopropyl-4-chlorophenylacetate |
| GB1582594A (en) * | 1976-04-23 | 1981-01-14 | Roussel Uclaf | Chiral acid esters |
| EP0107296A1 (en) * | 1982-10-18 | 1984-05-02 | Imperial Chemical Industries Plc | Insecticidal product and preparation thereof |
| US4997970A (en) * | 1987-06-15 | 1991-03-05 | Fmc Corporation | Conversion of pyrethroid isomers to move active species |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1062334A (en) * | 1963-09-19 | 1967-03-22 | Merck & Co Inc | Racemization of compounds containing an asymmetric quaternary carbon atom |
| FR2375161A1 (fr) * | 1976-04-23 | 1978-07-21 | Roussel Uclaf | Procede de transformation d'un ester d'acide chiral d'alcool secondaire a-cyane optiquement actif de structure (r) en ester d'acide chiral d'alcool secondaire a-cyane de structure (s) |
| GB1599876A (en) * | 1977-06-13 | 1981-10-07 | Shell Int Research | Conversion of a stereoisomer into its diastereoisomer |
| CH635563A5 (fr) * | 1977-07-07 | 1983-04-15 | Sumitomo Chemical Co | Procede pour la preparation d'un alpha-cyano-3-phenoxybenzyle optiquement actif. |
| US4308279A (en) * | 1979-06-06 | 1981-12-29 | Fmc Corporation | Crystalline, insecticidal pyrethroid |
| CA1162560A (en) * | 1980-04-23 | 1984-02-21 | Ronald F. Mason | Process for preparing cyclopropane carboxylic acid ester derivatives |
| JPS56167654A (en) * | 1980-05-28 | 1981-12-23 | Sumitomo Chem Co Ltd | Method for obtaining stereoisomeric mixture of more highly active phenylacetic ester derivative |
| JPS5762298A (en) * | 1980-10-01 | 1982-04-15 | Mitsubishi Chem Ind Ltd | Preparation of 17alpha-cyanosteroid |
| US4422978A (en) * | 1980-10-20 | 1983-12-27 | Sumitomo Chemical Company, Limited | Method for preparing optically active carboxylic acid esters |
| DE3369128D1 (en) * | 1982-10-11 | 1987-02-19 | Ici Plc | Insecticidal product and preparation thereof |
| CA1206483A (en) * | 1982-11-11 | 1986-06-24 | Johannes Van Berkel | Process for preparing cyclopropane carboxylic acid ester derivatives |
| DE3401483A1 (de) * | 1984-01-18 | 1985-07-25 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung bestimmter enantiomerenpaare von permethrinsaeure-(alpha)-cyano-3-phenoxy-4-fluor-benzyl-ester |
| GB8418331D0 (en) * | 1984-07-18 | 1984-08-22 | Ici Plc | Insecticidal ester |
| GB8422872D0 (en) * | 1984-09-11 | 1984-10-17 | Ici Plc | Insecticidal product |
-
1991
- 1991-12-24 GB GB919127355A patent/GB9127355D0/en active Pending
-
1992
- 1992-12-11 GB GB9225856A patent/GB2262737A/en not_active Withdrawn
- 1992-12-15 SK SK760-94A patent/SK281750B6/sk unknown
- 1992-12-15 RO RO94-01080A patent/RO114125B1/ro unknown
- 1992-12-15 BR BR9206983A patent/BR9206983A/pt not_active IP Right Cessation
- 1992-12-15 EP EP92924842A patent/EP0618896B1/en not_active Expired - Lifetime
- 1992-12-15 NZ NZ246081A patent/NZ246081A/en unknown
- 1992-12-15 AU AU30932/92A patent/AU679168B2/en not_active Ceased
- 1992-12-15 AT AT92924842T patent/ATE142617T1/de not_active IP Right Cessation
- 1992-12-15 KR KR1019940702213A patent/KR100249399B1/ko not_active IP Right Cessation
- 1992-12-15 UA UA94005435A patent/UA39862C2/uk unknown
- 1992-12-15 CZ CZ19941536A patent/CZ287245B6/cs not_active IP Right Cessation
- 1992-12-15 RU RU94031154A patent/RU2129536C1/ru active
- 1992-12-15 HU HU9401811A patent/HU214673B/hu not_active IP Right Cessation
- 1992-12-15 DK DK92924842.5T patent/DK0618896T3/da active
- 1992-12-15 CA CA002126180A patent/CA2126180C/en not_active Expired - Fee Related
- 1992-12-15 JP JP51123493A patent/JP3490083B2/ja not_active Expired - Fee Related
- 1992-12-15 ES ES92924842T patent/ES2091497T3/es not_active Expired - Lifetime
- 1992-12-15 DE DE69213761T patent/DE69213761T2/de not_active Expired - Lifetime
- 1992-12-15 WO PCT/GB1992/002323 patent/WO1993013053A2/en active IP Right Grant
- 1992-12-22 ZA ZA929971A patent/ZA929971B/xx unknown
- 1992-12-23 US US07/995,861 patent/US5334744A/en not_active Expired - Lifetime
- 1992-12-30 TW TW081110490A patent/TW318827B/zh not_active IP Right Cessation
-
1994
- 1994-06-21 FI FI942989A patent/FI114465B/fi not_active IP Right Cessation
- 1994-06-23 NO NO942400A patent/NO300678B1/no not_active IP Right Cessation
- 1994-06-24 BG BG98874A patent/BG61446B1/bg unknown
-
1996
- 1996-10-07 GR GR960402622T patent/GR3021271T3/el unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1582594A (en) * | 1976-04-23 | 1981-01-14 | Roussel Uclaf | Chiral acid esters |
| EP0002289A1 (en) * | 1977-09-26 | 1979-06-13 | Shell Internationale Researchmaatschappij B.V. | Process for converting a stereoisomeric ester into its diastereoisomer; crystalline (-)-S-alpha-cyano-3-phenoxybenzyl (+)-S-alpha-isopropyl-4-chlorophenylacetate |
| EP0107296A1 (en) * | 1982-10-18 | 1984-05-02 | Imperial Chemical Industries Plc | Insecticidal product and preparation thereof |
| US4997970A (en) * | 1987-06-15 | 1991-03-05 | Fmc Corporation | Conversion of pyrethroid isomers to move active species |
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